A Kinetic Electron Spin Resonance Study of the Transfer of a Hydrogen Atom from α-Tetralin Hydroperoxide to a Tertiary Alkylperoxy Radical

Chenier, J.H.B.; Howard, J.A.

Canadian Journal of Chemistry 53(5): 623-627

1975


ISSN/ISBN: 0008-4042
Accession: 081024570

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Abstract
A kinetic electron spin resonance spectroscopic study of the reaction of tertiary alkylperoxy radicals with α-tetralin hydroperoxide is reported. The absolute rate constants for this hydrogen atom transfer process (k 1 ) are given by the equation log (k 1 /M −1 s −1 ) = (6.0 ± 0.5 ) − (4.5 ± 0.5 )/θ, where θ = 2.303 RT kcal mol −1 .A significant isotope effect is obtained when the hydroperoxidic hydrogen is replaced by deuterium, e.g. k 1 H /k 1 D at 21° = 9.Other alkyl hydroperoxides, e.g. triphenylmethyl, s-butyl, and 9,10-dihydro-9-anthracyl have approximately the same reactivity to t-ROO • as α-C 10 H 11 OOH.